Methods and apparatus for controlling water hardness

ABSTRACT

The present invention is related to methods, apparatuses, and compositions for controlling water hardness. The methods, apparatuses and compositions also reduce scale formation. The present invention includes substantially water insoluble resin materials. The resin materials may be loaded with a plurality of cations.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No. 12/764,621filed on Apr. 21, 2010, which claims priority to provisional applicationof U.S. Ser. No. 61/261,610 filed Nov. 16, 2009 and provisionalapplication U.S. Ser. No. 61/171,145 filed Apr. 21, 2009, which arehereby incorporated by reference in their entireties.

FIELD OF THE INVENTION

The present invention relates to methods, apparatuses, and systems forcontrolling water hardness, and scale formation. In particular, theinvention relates to methods, apparatuses and systems that include asubstantially water insoluble resin material that aids in controllingwater hardness, without substantially altering the composition of thewater treated. Methods for inhibiting or reducing scale formation arealso provided. The present invention also relates to methods ofemploying treated water, for example, in cleaning processes.

BACKGROUND OF THE INVENTION

Detergents contain numerous components to improve the cleaning activityof the detergent. For example, detergents often contain components tocounteract the effects of water hardness. Hard water is known to reducethe efficacy of detergents, by forming films on surfaces, and reactingwith detergent components making them less functional in the cleaningprocess. Calcium is a divalent ion known to bind soils to surfaces,creating a film, and a making the soil more difficult to remove.

One method for counteracting this includes adding chelating agents orsequestrants into detersive compositions that are intended to be mixedwith hard water in an amount sufficient to handle the hardness. However,in many instances the water hardness exceeds the chelating capacity ofthe composition. As a result, free calcium ions may be available toattack active components of the composition, to cause corrosion orprecipitation, or to cause other deleterious effects, such as poorcleaning effectiveness or lime scale build up. Further, chelators andsequestrants (e.g., phosphates and NTA) have been found to causeenvironmental or health issues.

Another method for addressing water hardness issues currently used is tosoften water via ion exchange, e.g., by exchanging the calcium andmagnesium ions in the water with sodium associated with a resin bed in awater softening unit. The calcium and magnesium adhere to a resin in thesoftener. When the resin becomes saturated it is necessary to regenerateit using large amounts of sodium chloride dissolved in water. The sodiumdisplaces the calcium and magnesium, which is flushed out in a brinysolution along with the chloride from the added sodium chloride. Whenwater softeners regenerate they produce a waste stream that containssignificant amounts of chloride, including calcium and magnesium salts,creating a burden on the system, e.g., sewer system, in which they aredisposed of, including a multitude of downstream water re-useapplications like potable water usages and agriculture. Further,traditional water softeners add to the salt content in discharge surfacewaters, which has become an environmental issue in certain locations.

SUMMARY

In some aspects, the present invention relates to an apparatus fortreating a water source. The apparatus comprises an inlet for providingthe water to a first treatment reservoir. A water treatment compositioncomprising a substantially water insoluble resin material loaded with aplurality of one or more multivalent cations, is contained within thetreatment reservoir. The apparatus also includes an outlet fluidlyconnected to the first treatment reservoir, wherein the outlet providestreated water from the treatment reservoir. In some embodiments, thewater treatment composition does not precipitate water hardness ions outof a source of water when contacted with the water. In some embodiments,the apparatus is located in an automatic washing system. In otherembodiments, the apparatus is located upstream from an automatic washingmachine. The automatic washing machine is selected from the groupconsisting of an automatic ware washing machine, vehicle washing system,instrument washer, clean in place system, food processing cleaningsystem, bottle washer, and an automatic laundry washing machine in someembodiments.

In other aspects, the present invention relates to methods for treatingwater comprising contacting a water treatment composition comprising asubstantially water insoluble resin material loaded with a plurality ofone or more multivalent cations, with a water source.

In other aspects, the present invention relates to methods of using atreated water source to clean an article. The method includes treating awater source. The step of treating the water source comprises contactinga water treatment composition comprising a substantially water insolubleresin material loaded with a plurality of one or more multivalentcations with a water source to form a treated water source. The methodincludes forming a use solution with the treated water and a detergent,and contacting the article with the use solution such that the articleis cleaned.

In still yet other aspects, the present invention relates to methods forreducing scale formation in an aqueous system comprising contacting theaqueous system with a composition consisting essentially of asubstantially water insoluble resin material loaded with a plurality ofmultivalent cations, such that scale formation in the aqueous system isreduced.

In other aspects, the present invention relates to methods formanufacturing a water treatment device. The methods include: loading acomposition comprising a substantially water insoluble resin materialinto a treatment reservoir, wherein said treatment reservoir comprisesan inlet and an outlet; and exhausting the resin material, wherein saidstep of exhausting the resin material comprises loading a surface of theresin material with a plurality of multivalent cations.

In some aspects, the present invention relates to methods for reducingscale formation comprising providing about 10 to about 1000 parts perbillion of a substantially water insoluble resin material to a watersource, such that scale formation is reduced. In other aspects, thepresent invention relates to methods for reducing scale formation,comprising providing about 10 to about 1000 parts per billion of a watersoluble polymer material obtained from a substantially water insolubleresin material, to a water source.

In other aspects, the present invention relates to a water treatmentcomposition consisting essentially of a source of substantially waterinsoluble resin material, wherein said resin material is loaded with aplurality of cations selected from the group consisting of a source ofcolumn 1 a, 2 a or 3 a elements from the Periodic Table, wherein saidcations do not include calcium.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic of an exemplary water treatment apparatus of thepresent invention.

FIGS. 2A and 2B are photographs of test glasses washed with untreatedwater, water treated with a calcium bound resin, water treated with amagnesium bound resin, and water treated with a hydrogen bound resin.

FIG. 3 is a photograph of the results of a limescale test using watertreated in accordance with embodiments of the present invention,compared to water treated using a known water hardness precipitationdevice, and a control sample.

FIGS. 4A and 4B are photographs of test glasses in a 100 cycle testusing varying water treatments.

FIG. 5 is a photograph of test glasses in a 100 cycle test with a sourcealkalinity provided using varying water treatments.

FIG. 6 is a photograph of booster heater elements after a five day testrun with and without a point of use water treatment system in accordancewith embodiments of the present invention.

FIG. 7 is a graphical depiction of the total dissolved solids versustime as described in Example 6.

FIG. 8 is a graphical depiction of the permeate versus time as describedin Example 6.

FIG. 9 is a graphical depiction of the change in pH over time asdescribed in Example 7.

FIG. 10 is a graphical depiction of the amount of total dissolved solidsin parts per million over time as described in Example 7.

FIG. 11 is a graphical depiction of the amount of scaling measured on alight box as described in Example 8, with the addition of 1 part permillion chlorine.

FIG. 12 is a graphical depiction of the amount of scaling measured on alight box as described in Example 8, with the addition of 10 parts permillion chlorine.

FIG. 13 is a graphical depiction of the total organic carbon measuredwith the addition of 1 part per million chlorine as described in Example8.

FIG. 14 is a graphical depiction of the total organic carbon measuredwith the addition of 10 parts per million chlorine as described inExample 8.

FIG. 15 is a graphical depiction of the total organic carbon measured inparts per million of various exhausted resin materials with the additionof different oxidants as described in Example 8.

FIG. 16 is a graphical depiction of the total organic carbon measured inparts per million of various exhausted resin materials with the additionof varying levels of chlorine as described in Example 8.

FIG. 17 is a graphical depiction of the light box score for glassestreated with water from various exhausted resins as described in Example9.

FIG. 18A is a graphical depiction of the Gel Permeation Chromatographystudy described in Example 10.

DETAILED DESCRIPTION OF THE INVENTION

In some aspects, the present invention relates to an apparatus fortreating a water source, and methods of use thereof. The apparatus mayinclude a water treatment composition. Water treatment compositionssuitable for use in the present invention include a substantially waterinsoluble resin material. The resin material may be provided loaded witha plurality of multivalent cations. In other embodiments, the resinmaterial may be provided with a plurality of cations selected from thegroup consisting of alkali metal cations, alkali earth metal cations,metal cations from group Ma of the periodic table, and combinationsthereof. The apparatuses of the present invention are capable ofcontrolling water hardness, and reducing the formation of scale onsurfaces contacted with water treated using the apparatuses. However,unlike other water hardness controlling devices, the apparatuses of thepresent invention do not cause a substance to precipitate out ofsolution. Nor do the apparatuses of the present invention control waterhardness by ion exchange mechanisms.

So that the invention may be more readily understood certain terms arefirst defined.

As used herein, the terms “builder,” “chelating agent,” and“sequestrant” refer to a compound that forms a complex (soluble or not)with water hardness ions (from the wash water, soil and substrates beingwashed) in a specific molar ratio. Chelating agents that can form awater soluble complex include sodium tripolyphosphate, EDTA, DTPA, NTA,citrate, and the like. Sequestrants that can form an insoluble complexinclude sodium triphosphate, zeolite A, and the like. As used herein,the terms “builder,” “chelating agent,” and “sequestrant” aresynonymous.

As used herein, the term “free of chelating agent” or “substantiallyfree of chelating agent” refers to a composition, mixture, oringredients that does not contain a chelating agent or sequestrant or towhich only a limited amount of a chelating agent, builder, orsequestrant has been added. Should a chelating agent, builder, orsequestrant be present, the amount of a chelating agent, builder, orsequestrant shall be less than about 7 wt %. In some embodiments, suchan amount of a chelating agent, builder, or sequestrant is less thanabout 2 wt %, less then about 0.5 wt %, or less than about 0.1 wt %.

As used herein, the term “lacking an effective amount of chelatingagent” refers to a composition, mixture, or ingredients that containstoo little chelating agent, builder, or sequestrant to measurably affectthe hardness of water.

As used herein, the term “solubilized water hardness” refers to hardnessminerals dissolved in ionic form in an aqueous system or source, i.e.,Ca⁺⁺ and Mg⁺⁺. Solubilized water hardness does not refer to hardnessions when they are in a precipitated state, i.e., when the solubilitylimit of the various compounds of calcium and magnesium in water isexceeded and those compounds precipitate as various salts such as, forexample, calcium carbonate and magnesium carbonate.

As used herein, the term “water soluble” refers to a compound orcomposition that can be dissolved in water at a concentration of morethan 1 wt-%.

As used herein, the terms “slightly soluble” or “slightly water soluble”refer to a compound or composition that can be dissolved in water onlyto a concentration of 0.1 to 1.0 wt-%.

As used herein, the term “substantially water insoluble” or “waterinsoluble” refers to a compound that can be dissolved in water only to aconcentration of less than 0.1 wt-%. For example, magnesium oxide isconsidered to be insoluble as it has a water solubility (wt %) of about0.00062 in cold water, and about 0.00860 in hot water. Other insolublecompounds for use with the methods of the present invention include, forexample: magnesium hydroxide with a water solubility of 0.00090 in coldwater and 0.00400 in hot water; aragonite with a water solubility of0.00153 in cold water and 0.00190 in hot water; and calcite with a watersolubility of 0.00140 in cold water and 0.00180 in hot water.

As used herein, the term “threshold agent” refers to a compound thatinhibits crystallization of water hardness ions from solution, but thatneed not form a specific complex with the water hardness ion. Thisdistinguishes a threshold agent from a chelating agent or sequestrant.Threshold agents include a polyacrylate, a polymethacrylate, anolefin/maleic copolymer, and the like.

As used herein, the term “free of threshold agent” or “substantiallyfree of threshold agent” refers to a composition, mixture, or ingredientthat does not contain a threshold agent or to which only a limitedamount of a threshold agent has been added. Should a threshold agent bepresent, the amount of a threshold agent shall be less than about 7 wt%. In some embodiments, such an amount of a threshold agent is less thanabout 2 wt-%. In other embodiments, such an amount of a threshold agentis less then about 0.5 wt-%. In still yet other embodiments, such anamount of a threshold agent is less than about 0.1 wt-%.

As used herein, the term “antiredeposition agent” refers to a compoundthat helps keep a soil composition suspended in water instead ofredepositing onto the object being cleaned.

As used herein, the term “phosphate-free” or “substantiallyphosphate-free” refers to a composition, mixture, or ingredient thatdoes not contain a phosphate or phosphate-containing compound or towhich a phosphate or phosphate-containing compound has not been added.Should a phosphate or phosphate-containing compound be present throughcontamination of a phosphate-free composition, mixture, or ingredients,the amount of phosphate shall be less than about 1.0 wt %. In someembodiments, the amount of phosphate is less than about 0.5 wt %. Inother embodiments, the amount of phosphate is less then about 0.1 wt %.In still yet other embodiments, the amount of phosphate is less thanabout 0.01 wt %.

As used herein, the term “phosphorus-free” or “substantiallyphosphorus-free” refers to a composition, mixture, or ingredient thatdoes not contain phosphorus or a phosphorus-containing compound or towhich phosphorus or a phosphorus-containing compound has not been added.Should phosphorus or a phosphorus-containing compound be present throughcontamination of a phosphorus-free composition, mixture, or ingredients,the amount of phosphorus shall be less than about 1.0 wt %. In someembodiments, the amount of phosphorous is less than about 0.5 wt %. Inother embodiments, the amount of phosphorus is less than about 0.1 wt %.In still yet other embodiments, the amount of phosphorus is less thanabout 0.01 wt %.

“Cleaning” means to perform or aid in soil removal, bleaching, microbialpopulation reduction, or combination thereof.

As used herein, the term “ware” refers to items such as eating andcooking utensils and dishes, and other hard surfaces such as showers,sinks, toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, and floors. As used herein, the term “warewashing” refers towashing, cleaning, or rinsing ware.

As used herein, the term “hard surface” includes showers, sinks,toilets, bathtubs, countertops, windows, mirrors, transportationvehicles, floors, and the like.

As used herein, the phrase “health care surface” refers to a surface ofan instrument, a device, a cart, a cage, furniture, a structure, abuilding, or the like that is employed as part of a health careactivity. Examples of health care surfaces include surfaces of medicalor dental instruments, of medical or dental devices, of autoclaves andsterilizers, of electronic apparatus employed for monitoring patienthealth, and of floors, walls, or fixtures of structures in which healthcare occurs. Health care surfaces are found in hospital, surgical,infirmity, birthing, mortuary, and clinical diagnosis rooms. Thesesurfaces can be those typified as “hard surfaces” (such as walls,floors, bed-pans, etc.), or fabric surfaces, e.g., knit, woven, andnon-woven surfaces (such as surgical garments, draperies, bed linens,bandages, etc.), or patient-care equipment (such as respirators,diagnostic equipment, shunts, body scopes, wheel chairs, beds, etc.), orsurgical and diagnostic equipment. Health care surfaces include articlesand surfaces employed in animal health care.

As used herein, the term “instrument” refers to the various medical ordental instruments or devices that can benefit from cleaning using watertreated according to the methods of the present invention.

As used herein, the phrases “medical instrument,” “dental instrument,”“medical device,” “dental device,” “medical equipment,” or “dentalequipment” refer to instruments, devices, tools, appliances, apparatus,and equipment used in medicine or dentistry. Such instruments, devices,and equipment can be cold sterilized, soaked or washed and then heatsterilized, or otherwise benefit from cleaning using water treatedaccording to the present invention. These various instruments, devicesand equipment include, but are not limited to: diagnostic instruments,trays, pans, holders, racks, forceps, scissors, shears, saws (e.g. bonesaws and their blades), hemostats, knives, chisels, rongeurs, files,nippers, drills, drill bits, rasps, burrs, spreaders, breakers,elevators, clamps, needle holders, carriers, clips, hooks, gouges,curettes, retractors, straightener, punches, extractors, scoops,keratomes, spatulas, expressors, trocars, dilators, cages, glassware,tubing, catheters, cannulas, plugs, stents, scopes (e.g., endoscopes,stethoscopes, and arthoscopes) and related equipment, and the like, orcombinations thereof.

As used herein, the term “laundry,” refers to woven and non-wovenfabrics, and textiles. For example, laundry can include, but is notlimited to, clothing, bedding, towels and the like.

As used herein, the term “water source,” refers to any source of waterthat can be used with the methods, systems and apparatus of the presentinvention. Exemplary water sources suitable for use in the presentinvention include, but are not limited to, water from a municipal watersource, or private water system, e.g., a public water supply or a well.The water can be city water, well water, water supplied by a municipalwater system, water supplied by a private water system, and/or waterdirectly from the system or well. The water can also include water froma used water reservoir, such as a recycle reservoir used for storage ofrecycled water, a storage tank, or any combination thereof. In someembodiments, the water source is not an industrial process water, e.g.,water produced from a bitumen recovery operation. In other embodiments,the water source is not a waste water stream.

The methods, systems, apparatuses, and compositions of the presentinvention can include, consist essentially of, or consist of thecomponents and ingredients of the present invention as well as otheringredients described herein. As used herein, “consisting essentiallyof” means that the methods, systems, apparatuses and compositions mayinclude additional steps, components or ingredients, but only if theadditional steps, components or ingredients do not materially alter thebasic and novel characteristics of the claimed methods, systems,apparatuses, and compositions.

As used herein, “weight percent,” “wt-%,” “percent by weight,” “% byweight,” and variations thereof refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

As used herein, the term “about” or “approximately” refers to variationin the numerical quantity that can occur, for example, through typicalmeasuring and liquid handling procedures used for making concentrates oruse solutions in the real world; through inadvertent error in theseprocedures; through differences in the manufacture, source, or purity ofthe ingredients used to make the compositions or carry out the methods;and the like. The term “about” also encompasses amounts that differ dueto different equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to a composition containing “a compound” includes acomposition having two or more compounds. It should also be noted thatthe term “or” is generally employed in its sense including “and/or”unless the content clearly dictates otherwise.

Water Treatment Apparatus

The present invention relates to apparatuses, compositions, and methodsfor use in controlling water hardness. In some aspects, the apparatusesand compositions of the present invention include a substantially waterinsoluble resin material. Without wishing to be bound by any particulartheory it is thought that the compositions and apparatuses control waterhardness without substantially altering the water source. That is, it isthought that the compositions and apparatuses of the present inventiondo not precipitate a substance out of the water, nor do they controlwater hardness via a conventional ion exchange mechanism. Further, theapparatuses do not substantially alter the pH or total dissolved solids(TDS) of the water source treated.

Water treated in accordance with the methods and apparatuses of thepresent invention has many beneficial effects, including, but notlimited to: reduction of scale and soiling in areas where hard water cancause soiling: protecting equipment, e.g., industrial equipment, fromscale build up: increased cleaning efficacy when used with conventionaldetersive compositions: and reducing the need for specific chemistries,e.g., those containing threshold agents, chelating agents, orsequestrants, or phosphorous, in downstream cleaning processes.

In some aspects, the apparatuses and compositions of the presentinvention include a water treatment composition. The water treatmentcompositions may be in a variety of physical forms. For example, thewater treatment composition may be in the form of a sheet, a bead, or amembrane.

In some embodiments, the water treatment composition includes asubstantially water insoluble resin material. A variety of resinmaterials may be used with the apparatuses of the present invention.

In some embodiments, the resin material is an exhausted resin material.As used herein, the term “exhausted resin material” refers to an ionexchange resin material that can control water hardness, but that isincapable of performing an ion exchange function. In some embodiments,an exhausted resin material has a surface that is substantially loadedwith a plurality of one or more multivalent cations, and is thus unableto exchange ions with a water source when contacted with a water source.The exhausted resin materials of the present invention do not controlwater hardness through an ion exchange mechanism. That is, the surfaceof an exhausted resin material is inert, as it is loaded with aplurality of multivalent cations.

The water treatment composition may include a resin substantially loadedwith a plurality of one or more multivalent cations. As used herein, theterm “multivalent cations” refers to cations having a valency of 2 orhigher. In some embodiments, the multivalent cations include a mixtureof calcium and magnesium ions. The calcium and magnesium ions may beloaded on to the resin material at a ratio of from about 1:10 to about10:1, about 1:5 to about 5:1, about 1:3 to about 3:1, about 1:2 to about2:1, or from about 1:1 of calcium ions to magnesium ions. In someembodiments, the mixture includes a 2:1 ratio of calcium to magnesiumions.

In other aspects, the water treatment composition includes asubstantially water insoluble resin material, wherein the resin materialis loaded with a plurality of cations. The cations may be selected fromthe group consisting of a source of column 1 a, 2 a or 3 a elements fromthe Periodic Table. In some embodiments, the cations do not includecalcium. In some embodiments, the cations are selected from the groupconsisting of hydrogen ions, sodium ions, magnesium ions, aluminum ions,zinc ions, titanium ions, and mixtures thereof. The resins for use inthe present invention may include, or exclude, any one or more than oneof these cations.

In some embodiments, the resin material includes an acid cation exchangeresin. The acid cation exchange resin may include a weak acid cationexchange resin, a strong acid cation exchange resin, and combinationsthereof. Weak acid cation exchange resins suitable for use in thepresent invention include, but are not limited to, a crosslinked acrylicacid polymer, a crosslinked methacrylic acid polymer, and mixturesthereof. In some embodiments, resin polymers have additional copolymersadded. The copolymers include but are not limited to butadiene,ethylene, propylene, acrylonitrile, styrene, vinylidene chloride, vinylchloride, and derivatives and mixtures thereof.

Commercially available weak acid cation exchange resins are available,and include but are not limited to: C-107 available from Purolite;Amberlite IRC 76 available from Dow; Lewatit CNP 80 WS available formLanxess; and MAC-3 available from Dow.

Without wishing to be bound by any particular theory, it is thought thatin some embodiments, the resin material provides to the water source asubstantially low molecular weight polymer material. In someembodiments, the resin material is an acrylic acid polymer that providesa polyacrylate material having a molecular weight of about 150 to about100,000 to the water source. In other embodiments, the resin materialprovides a polyacrylate material having a relatively low molecularweight of less than about 20,000 to the water source.

The resin material may be provided in any shape and size, includingbeads, rods, disks or combinations of more than one shape. In someembodiments, the resin material is selected from the group consisting ofa gel type resin structure, a macroporous type resin structure, andcombinations thereof. Without wishing to be bound by any particulartheory it is thought that the resin particle size may affect the abilityof the resin material to control water hardness. For example, in someembodiments, the resin material may have a particle size of from about0.5 mm to about 1.6 mm. In other embodiments, the resin material mayhave a particle size as large of 5.0 mm. The resin material may alsoinclude a mixture of particle sizes, viz. a mixture of large and smallparticles.

Other factors that are thought to have an effect on the ability of theresin material to control water hardness include, but are not limitedto, the particle size distribution, the amount of cross linking, and thepolymers used. In some embodiments, the ability of the resin material tocontrol water hardness is impacted by whether there is a narrow particlesize distribution, e.g., a uniformity coefficient of 1.2 or less, or awide (Gaussian) particle size distribution, e.g., a uniformitycoefficient of 1.5 to 1.9.

Further, it is thought that the selectivity of the resin can be modifiedto tailor the resin to have an affinity for one ion over another. Forexample, the amount of cross linking and type of polymers included inthe resin are thought to impact the selectivity of the resin. Aselective affinity for particular ions over other ions may be beneficialin situations where a high affinity for certain ions, e.g., copper, maybe damaging, e.g., foul or poison, to the resin itself. The resinmaterial may bind cations by a variety of mechanisms including, but notlimited to, by ionic or electrostatic force.

In some embodiments, an acrylic acid polymer resin material iscrosslinked with a polyvinyl aromatic composition. Suitable polyvinylaromatic compositions for use in the present invention include divinylbenzene, trivinyl benzene, divinyl toluene, divinyl xylene, polyvinylanthracene, and derivatives and mixtures thereof. In some embodiments,the crosslinked acrylic acid polymer is about 0.5% to about 25%crosslinked. In other embodiments, the acrylic acid polymer is less thanabout 8%, less than about 4% or less than about 2% crosslinked.

In some embodiments, the resin includes a weak acid cation exchangeresin having H+ions attached to the active sites. The resin may then beexhausted, viz. loaded with a plurality of multivalent cations by any ofa variety of methods, e.g., by having a water source run over it. Insome embodiments, the plurality of multivalent cations includes, but isnot limited to, the calcium and magnesium present in the water source.Without wishing to be bound by any particular theory, it is thought thatas the water runs over the resin, the calcium and magnesium ions in thewater will attach to the resin, thereby neutralizing it. At this pointthe resin is exhausted as it can no longer exchange ions with the watersource.

An example of a water treatment apparatus for use in the presentinvention is shown in FIG. 1. A schematic of a water treatment apparatusis shown at reference 10. The apparatus includes: an inlet 12 forproviding the water source to a treatment reservoir 14; a treatmentreservoir 14 including a water treatment composition 16; an outlet 18for providing treated water from the treatment reservoir; and a treatedwater delivery line 20. In some embodiments, the treated water deliveryline 20 provides water to a selected washing system. In otherembodiments, the treated water delivery line 20 provides water to anadditional water treatment apparatus. In some embodiments, there is nofilter between the outlet and the treated water delivery line. A flowcontrol device 22 such as a valve 24 can be provided in the treatedwater delivery line 20 to control the flow of the treated water into theselected end use device, e.g., a washing system, or another watertreatment device, e.g., a carbon filter, a reverse osmosis filter.

In some embodiments, the water treatment composition is contained withina treatment reservoir. Any reservoir capable of holding the watertreatment composition may be used as a treatment reservoir. Thereservoir can be for example, a tank, a cartridge, a filter bed ofvarious physical shapes or sizes, or a column. In other embodiments, thetreatment reservoir can include a mesh bag containing the watertreatment composition. In still yet other embodiments, the resinmaterial may be attached or adhered to a solid substrate. The substratecan include, but is not limited to, a flow-through filter type pad, orpaper. The substrate can also be a particulate that can be fluidized.

The treatment reservoir may include an inlet for providing water to thetreatment reservoir and an outlet for providing treated water to adesired end use location, e.g., a washing device, another watertreatment device. In some embodiments, the inlet is located at thebottom of the reservoir, and the outlet is located at the top of thereservoir. This allows for the water to flow up through the watertreatment composition contained within the treatment reservoir.

In some embodiments, the treatment reservoir includes an agitated bed ofthe water treatment composition. Methods for agitating the compositioninclude, for example, flow of water through a column, by fluidization,mechanical agitation, air sparge, eductor flow, baffles, flowobstructers, static mixers, high flow backwash, recirculation, andcombinations thereof. The treatment reservoir can further include a headspace above the composition contained therein, in order to allow for amore fluidized bed. In some embodiments, the resin material has adensity slightly higher than the density of water to maximizefluidization and/or agitation of the resin material.

In some embodiments, the inlet can further include a pressurized spraynozzle or eductor nozzle. The spray nozzle can provide the water at anincreased force to the treatment reservoir. This increased pressurizedforce can increase the agitation of the water treatment composition andcan circulate the resin through the eductor nozzle. In some embodiments,the spray nozzle provides the water to the treatment reservoir at a rateof about 5 feet per minute to about 200 feet per min.

The water treatment apparatuses of the present invention are designed tohandle increased water velocities compared to conventional ion exchangewater softeners. For example, a conventional ion exchange device isdesigned for a flow rate of about 0.3 to about 3.0 feet per minute ofwater velocity. This flow rate is important to allow time for thediffusion of ions to the surface of the resin from the water for the ionexchange process to occur. Without wishing to be bound by any particulartheory, it is thought that because the present water treatment apparatusdoes not operate by an ion exchange mechanism, the flow rate can beincreased through the apparatus. That is, a sufficient amount of timefor an ion exchange to occur is not necessary using an exemplaryapparatus of the present invention. For example, in some embodiments,the apparatuses of the present invention have a flow through rate ofabout 5 to about 200 feet per minute, about 20 to about 175 feet perminute, or about 50 to about 150 feet per minute.

In some embodiments, the treatment reservoir includes a portable,removable cartridge. The apparatuses of the present invention cancontrol water hardness while requiring a lower amount of water treatmentcomposition in the treatment reservoir compared to conventional watertreatment devices, e.g., ion exchange devices. For example, in someembodiments, the bed depth of the composition in the treatment reservoiris less than about 2 feet, or less than about 1.5 feet. Conventionalweak acid resins used in ion exchange water softening applications aredesigned for bed depths of 2.6 feet for water treatment rates of about 2to about 20 gallons per minute.

The apparatuses of the present invention can include one or moretreatment reservoirs. For example, two, three or four treatmentreservoirs containing the same or different water treatment compositionscan be used. The one or more treatment reservoirs can be provided in anyarrangement, for example, they may be provided in series, or inparallel.

In some embodiments, the entire treatment reservoir can be removable andreplaceable. In other embodiments, the treatment reservoir can beconfigured such that water treatment composition contained within thetreatment reservoir is removable and replaceable. In some embodiments,the treatment reservoir includes a removable, portable, exchangeablecartridge including a water treatment composition.

In some embodiments, an additional functional ingredient may be includedin the treatment reservoir. The additional functional ingredients can beincluded within the treatment reservoir, or they can be provided to thetreatment reservoir from an external source, e.g., an additionalfunctional ingredient inlet. The additional functional ingredients canbe added directly to the water source to be treated prior to the watersource entering the treatment apparatus. Alternatively, the additionalingredient can be added to the treatment reservoir prior to the watersource being passed through the reservoir.

Additional functional ingredients suitable for use with the apparatus ofthe present invention include any materials that impart beneficialproperties to the water treatment composition, the water source beingtreated, or any combination thereof. For example, functional ingredientsmay be added that aid in the prevention of “cementing” of the catalyst,i.e., agglomeration of the particles, as it is contacted with a watersource.

In some embodiments, an oxidant is included as an additional functionalingredient. Oxidants for use with the apparatus and methods of theinvention include, but are not limited to, halogens and substances richin halogen elements. Exemplary oxidants for use with the apparatus andmethods of the present invention include, but are not limited to,oxygen, ozone, chlorine sources including hypochlorite, fluorine,iodine, bromine, various peroxides including hydrogen peroxide, nitricacid and nitric oxide. In other embodiments, a gaseous oxidant isprovided to the water source before, or at substantially the same timeas the water source enters the treatment apparatus. For example, aircontaining oxygen can be injected into the water source prior to theapparatus via an air pump or aspirator.

Methods of Use

In some aspects, the present invention provides methods for controllingwater hardness and/or reducing scale formation. The methods may includecontacting a water treatment composition comprising a substantiallywater insoluble resin material with a water source. In some embodiments,the water treatment composition is contained within a treatmentreservoir. In other embodiments, the water treatment composition isloaded with a plurality of multivalent cations.

The step of contacting can include, but is not limited to, running thewater source over or through the water treatment composition. The watertreatment composition may be contained within a treatment reservoir,e.g., a column, cartridge, mesh bag or tank, of an apparatus of thepresent invention. The contact time is dependent on a variety offactors, including, for example, the pH of the water source, thehardness of the water source, and the temperature of the water source.

In some embodiments, the method includes heating the water source priorto the step of contacting the composition. Any means of heating thewater source may be used with the methods and apparatuses of the presentinvention. In some embodiments, the water is heated to a temperature ofabout 30° C. to about 90° C.

In other embodiments, the methods of the present invention may includethe step of increasing the pH of the water source. The step ofincreasing the pH of the water source may occur prior to the step ofcontacting the water treatment composition, during the step ofcontacting the composition, or both prior to and during the step ofcontacting the composition. For example, to increase the pH of the watersource prior to the step of contacting the water treatment composition,a source of calcite may be added to the water source. To increase the pHof the water source during the step of contacting, a source of calcitemay be added to the treatment reservoir. The pH of the water source maybe increased, for example, to a pH of about 8 to about 10.

The methods, apparatuses, and compositions of the invention may be usedfor a variety of purposes. For example, an apparatus for employing thewater treatment methods of the present invention can be connected to thewater main of a house or business. The apparatus can be employed in linebefore the hot water heater, or after the hot water heater. Thus, anapparatus of the present invention can be used to control water hardnessand/or reduce scale formation in hot, cold and room temperature watersources.

Once the water has been treated, the treated water may be provided to anautomatic washing machine from the treated water delivery line of theapparatus. The apparatus can be located in a variety of locationsrelative to the washing machine. For example, the apparatus may beupstream from the feed line of the washing machine, or within thewashing machine. Exemplary automatic washing machines suitable for usewith the apparatuses and methods of the present invention include, butare not limited to, an automatic ware washing machine, a vehicle washingsystem, an instrument washer, a clean in place system, a food processingcleaning system, a bottle washer, and an automatic laundry washingmachine. Alternatively, the treated water may be used in a manualwashing system. Any automatic washing machine or manual washing processthat would benefit from the use of water treated in accordance with themethods of the present invention can be used.

The water treatment methods and apparatuses of the present invention canbe used in a variety of industrial and domestic applications. The watertreatment methods and apparatuses can be employed in a residentialsetting or in a commercial setting, e.g., in a restaurant, hotel,hospital. For example, a water treatment method, system, or apparatus ofthe present invention can be used in: ware washing applications, e.g.,washing eating and cooking utensils and dishes, and other hard surfacessuch as showers, sinks, toilets, bathtubs, countertops, windows,mirrors, and floors; in laundry applications, e.g., to treat water usedin an automatic textile washing machine at the pre-treatment, washing,souring, softening, and/or rinsing stages; in vehicle care applications,e.g., to treat water used for pre-rinsing, e.g., an alkaline presoakand/or low pH presoak, washing, polishing, and rinsing a vehicle;industrial applications, e.g., cooling towers, boilers, industrialequipment including heat exchangers; in food service applications, e.g.,to treat water lines for coffee and tea brewers, espresso machines, icemachines, pasta cookers, water heaters, booster heaters, steamers and/orproofers; in healthcare instrument care applications, e.g., soaking,cleaning, and/or rinsing surgical instruments, treating feedwater toautoclave sterilizers; and in feedwater for various applications such ashumidifiers, hot tubs, and swimming pools. In some embodiments, anapparatus of the present invention can be used to treat water providedto an ice machine.

In some embodiments, the water treatment methods and systems of thepresent invention can be applied at the point of use. That is, a watertreatment composition, method, system, or apparatus of the presentinvention can be applied to a water source upstream of an applicationsuch as a washing system. In some embodiments, the water treatment isapplied immediately prior to the desired end use of the water source.For example, an apparatus of the present invention could be employed toa water line connected to a household or restaurant appliance, e.g., acoffee maker, an espresso machine, an ice machine. An apparatusemploying the methods of the present invention may also be located in awashing system.

Apparatuses of the present invention can also be included as part of anappliance which uses a water source, e.g., a water treatment systembuilt into an automatic or manual washing system, a coffee maker, an icemachine, a steam table, a booster heater, a grocery mister, ahumidifier, or any other system which may benefit from the use oftreated water. The apparatuses of the present invention can be used withany appliance or device which can provide a water source that wouldbenefit from treatment using the apparatuses of the present invention.For example, the apparatuses can be used with a hose, e.g., a gardenhose, or treat water that is provided to an electrolytic cell.

In some embodiments, an apparatus of the present invention including atreatment reservoir may be used with a washing machine in a variety ofways. In some embodiments, the treatment reservoir may be connected to adetergent dispensing device. The treatment reservoir may be used tosupply treated water to a washing system and/or to a rinsing system of awashing machine. In some embodiments, the treatment reservoir may beused to supply a mixture of treated water and detergent to a washingsystem.

In some embodiments, treated water can be combined with a detersivecomposition and the combination provided to a washing machine as a usesolution. Use of a treated water source has many advantages indownstream cleaning processes compared to use of a non-treated watersource. For example, use of a water source treated in accordance withthe methods of the present invention increases the efficacy ofconventional detergents. It is known that hardness ions combine withsoap and detergents to form a scale or scum. Further, hardness ionslimit the amount of lather formed with soaps and detergents. Withoutwishing to be bound by any particular theory, it is thought that byreducing the amount of these hardness ions the amount of thesedetrimental side effects can be reduced.

Further, use of a treated water source also allows for the use ofspecific environmentally friendly detersive compositions, e.g., thosesubstantially free of or free of builders, chelants, or sequestrants, orphosphorous.

Any detersive composition can be used with water treated according tothe present invention. For example, a cleaning composition, a rinseagent composition or a drying agent composition can be combined withtreated water to form a use solution. The articles to be cleaned and/orrinsed are then contacted with the use solution. Exemplary detergentcompositions include warewashing detergent compositions, laundrydetergent compositions, CIP detergent compositions, environmentalcleaning compositions, hard surface cleaning compositions (such as thosefor use on counters or floors), motor vehicle washing compositions, andglass cleaning compositions. Exemplary rinse agent compositions includethose compositions used to reduce streaking or filming on a surface suchas glass. Exemplary drying agent compositions include dewateringcompositions. In the vehicle washing industry, it is often desirable toinclude a dewatering step where a sheeting or beading agent is appliedto the vehicle exterior.

In some embodiments, the detersive composition for use with the methodsof the present invention includes a detergent that is substantially freeof a chelant, builder, sequestrant, and/or threshold agent, e.g., anaminocarboxylic acid, a condensed phosphate, a phosphonate, apolyacrylate, or the like. Without wishing to be bound by any particulartheory, it is thought that because the methods and apparatus of thepresent invention reduce the negative effects of hardness ions in thewater source, when used with a detergent, there is a substantiallyreduced or eliminated need to include chelating agents, builders,sequestrants, or threshold agents in the detergent composition in orderto handle the hardness ions.

In some embodiments, the detersive composition may include otheradditives, including conventional additives such as bleaching agents,hardening agents or solubility modifiers, defoamers, anti-redepositionagents, threshold agents, stabilizers, dispersants, enzymes,surfactants, aesthetic enhancing agents (i.e., dye, perfume), and thelike. Adjuvants and other additive ingredients will vary according tothe type of composition being manufactured. It should be understood thatthese additives are optional and need not be included in the cleaningcomposition. When they are included, they can be included in an amountthat provides for the effectiveness of the particular type of component.

In some embodiments, the apparatuses and methods of the presentinvention may be used to treat water that is then provided to anotherwater treatment device. That is, in some embodiments, an apparatus ofthe invention is located upstream from a water treatment device.Exemplary water treatment devices include, but are not limited to, areverse osmosis water treatment device, a heat exchange water treatmentdevice, a carbon filter, and mixtures thereof.

In some aspects, the present invention also provides methods formanufacturing a water treatment device of the present invention. Themethods include loading a water treatment composition including asubstantially water insoluble resin material into a treatment reservoir.The treatment reservoir includes an inlet and an outlet. The methodsfurther include exhausting the resin material. The step of exhaustingthe resin material may include loading a surface of the resin materialwith a plurality of multivalent cations.

In other aspects, the present invention provides methods for reducingscale formation. The methods include providing an effective amount of asubstantially water insoluble resin material to a water source such thatscale formation is reduced when an article is contacted with the treatedwater source. In some embodiments, an effective amount of asubstantially water insoluble resin includes about 10 to about 4000,about 10 to about 2000, about 10 to about 1000, or about 10 to about 600parts per billion of the material. In some embodiments, the effectiveamount is a non-thickening amount. That is, an amount that if providedin a detergent use solution, would not substantially thicken thedetergent use solution.

In other aspects, the present invention provides methods for reducingscale formation including providing an effective amount of a watersoluble polymer material. In some embodiments, the polymer material isobtained from a water treatment composition, e.g., a substantially waterinsoluble resin material. In other embodiments, the polymer materialcomprises a polyacrylate material. In some embodiments, the polyacrylatematerial includes a substantially low molecular weight polyacrylatematerial to the water source. In some embodiments, an effective amountof the water soluble low molecular weight polymer material includesabout 10 to about 4000, about 10 to about 2000, about 10 to about 1000,or about 10 to about 600 parts per billion of the material. In otherembodiments, the effective amount is a non-thickening amount. That is,an amount that if provided in a detergent use solution, would notsubstantially thicken the detergent use solution.

EXAMPLES

The present invention is more particularly described in the followingexamples that are intended as illustrations only. Unless otherwisenoted, all parts, percentages, and ratios reported in the followingexamples are on a weight basis, and all reagents used in the exampleswere obtained, or are available, from the chemical suppliers describedbelow, or may be synthesized by conventional techniques.

Example 1

Three 1 pound resin samples were prepared by loading them with H+, Ca++,and Mg++. The magnesium loaded sample was prepared according to thefollowing procedure. A weak acid cation resin, Lewatit S 8528 obtainedfrom the Lanxess Company, was soaked is 500 grams of NaOH beads and 2500ml of softened water for 24 hours. The pH was approximately 12-13. Aftersoaking, the resin was then rinsed thoroughly with softened water threetimes until the pH of the rinse water was below 11. The resin was soakedin 2500 ml of softened water with 700 grams of a MgCl₂.6H₂0 compositionfor 4 days. The resin was thoroughly rinsed with softened water threetimes. The final pH of the rinse water was approximately 7.5-8.5.

To load the resin with Ca++, the same procedure was used as describedabove for the MG++ resin, only the resin was soaked with CaCl₂composition. The H+ form of the resin, was the resin itself, without anycations loaded onto it.

Water was then treated with each of the resin samples and compared forscaling tendencies in a warewashing machine. The feedwater to thedishmachine was thus treated with a H+ weak acid cation resin, a Ca++weak acid cation resin, or a Mg++ weak acid cation resin in threeseparate but equivalent tests. Each of the resin samples were firstpre-conditioned by running hard (17 gpg) water through a flow-throughreservoir to drain. After approximately 1000 gallons of water flow, theresin/reservoir systems were connected to the dishmachine and evaluatedfor scaling tendencies on glassware. The results of this comparison testare shown in FIG. 2A. After this dishmachine/glassware scaling test, theresin samples were further conditioned by running hard water through aflow-through reservoir to drain for an additional 4000 gallons andtherefore each resin had treated a total of about 5000 gallons of water.The resin was confirmed to be exhausted of capacity at this point bymeasuring the water hardness of the water, i.e., the calcium andmagnesium amounts in the water were the same after treatment, as beforetreatment.

A second set of dishmachine/glassware scaling tests were then conducted,again without detergent and those results are shown in FIG. 2B.

The control glasses (not shown) had heavy scale. The first two glassesfrom the left in each FIGS. 2A and 2B were treated with H+ bound resin.The third and fourth glass from the left in each figure were treatedwith Ca2+ bound resin, and the fifth and sixth glass from the left ineach figure were treated with a Mg2+ bound resin. As seen in FIG. 2A,the H+ resin and the Mg2+ resin showed no visible scale in the testusing resin that had previously treated 1000 gallons of water. The twoCa2+ resin showed a clearly visible scale. Referring to FIG. 2B, inwhich each of the resin systems had previously treated 5000 gallons ofwater, the H+ resin resulted in a slight scale on the glassware. TheCa2+ resin showed a slightly heavier scale, and the Mg2+ resin showedlittle or no visible scale.

Example 2

Water with 17 grains of water hardness was treated with two pounds ofWatts OneFlow media, commercially available from Watts, at a rate ofabout 5 gallons per minute. In addition, water with 17 grains of waterhardness was treated with a magnesium loaded weak acid resin accordingto the present invention at the same conditions. An alkalinity sourceincluding 800 ppm of sodium carbonate was added to each of these watersamples, as well as to a control sample of untreated water. The resultsare shown in FIG. 3. As can be seen from this Figure, both the controland the Watts treated water had a signification precipitation of waterhardness. The water treated according to the present invention (shown asthe right most beaker) showed no signs of a precipitate.

Example 3

A test was run to measure the limescale build up control using variouscommercially available water treatment materials. Two separate testswere run. The first test was a 100 cycle dishmachine test. A door typedishmachine (Hobart AM-15) was used. The selected test apparatus wasconnected to the inlet water to the dishmachine so that all of the rinsewater for the machine was treated. The inlet water had a hardness of 17grains. Glassware was placed inside the dishmachine in a glassware rack.The machine was run normally for 100 cycles. No chemicals, e.g.,detergents, rinse aids, other than the treatment apparatuses were usedin this test. After the 100 cycles were complete, the glassware wasremoved and allowed to air dry. Photos of the glasses were taken. Alight box was used to determine reflectance which is a directcorrelation to the amount of scale present. The photos and light boxscores were compared for the different water treatments tested. A lightbox score differing by 10,000 is considered significant.

For this 100 cycle test the following media were tested: Amberlite IRC76 commercially available from Dow; Lewatit S-8528, commerciallyavailable from Lanxess; Watts OneFlow Media, commercially available fromWatts; and Filtersorb SP3, commercially available from CWG USA. Theresults are shown in FIGS. 4A and 4B.

As can be seen from these Figures, relatively good results, viz. lowscaling, were achieved using the IRC-76 and Lanxess resins. As is seenin FIG. 4B, poor results were achieved using the Watts and Filtersorbmaterials.

Another test was run to measure the limescale control in applicationswhere cleaning chemicals are present. This test was run similar to theprotocol for the 100 cycle test described above, however, 850 ppm ofsodium carbonate was added to the wash tank of the dishmachine. Thislevel of alkalinity was maintained throughout the test. Also, the testwas only run for 10 cycles.

The results of this test are shown in FIG. 5. As can be seen from thisFigure, better results were obtained using the exhausted IRC-76 andLanxess resins compared to the OneFlow and SP-3 media.

Example 4

An experiment was run to determine the ability of a substance to preventscaling in hard water under alkaline conditions. A test substance wasformed by combining 17 grain hard water with 0.4 mg of a substanceremoved from a used Mg+ loaded resin (a resin as described above inExample 1). Without wishing to be bound by any particular theory, it isthought that the substance removed from the resin included organicmaterial that includes, at least in part, a polyacrylate material.Although manually removed, viz. extracted from the resin surface, forthe purposes of this example, it is thought that in practice thismaterial would be removed from the resin by the flow of water over andthrough the resin. The 0.4 mg removed was equivalent to 800 parts perbillion of this material. 0.1 grams of dense ash (200 ppm ash) was addedto this solution. The solution was stirred and observed for scaleformation, e.g., cloudiness of the solution. The test solution wascompared to a control solution containing only 17 grain hard water andan equivalent amount of ash as the test solution. The solutions wereobserved at two and five minutes. At the two minute time point, the testsolution remained clear, while the control solution had a cloudy, whiteappearance. At the five minute time point, the test solution was slightcloudier than it originally appeared, but was still much clearer thanthe control solution, which had increased in cloudiness.

Example 5

A test was run to determine the effect of a water treatment apparatus asa point of use treatment for booster heaters. In this test, two boosterheaters were run concurrently. One booster heater used 17 grain pergallon water. The second booster heater used 17 grain per gallon waterwhich was pretreated with the water treatment apparatus. Both boosterheaters were run for five consecutive days. They were programmed with arepeating pattern of “on” for three hours followed by three hours ofdown time. During the three “on” hours, water was run through thebooster heater at 5 gallons per minute for one minute, followed by oneminute of zero flow. During this “on” time, the booster heater was setto heat the water to a temperature of 185° F.

The results are shown in FIG. 6. As can be seen in this figure, thebooster heater that used treated water had far less scaling than thecontrol booster heater. The amount of scale on the elements and thethickness of the scale were substantially reduced with the treated watercompared to the control.

Example 6

A test was run to evaluate the effects of water treated with anapparatus in accordance with embodiments of the present invention whenused with a reverse osmosis membrane. A five gallon bucket was filledwith either treated or non-treated 17 grain per gallon water. Treatedwater was water that had been run through two 0.75 pound cartridgescontaining an exhausted ion exchange resin material. The ion exchangematerial was exhausted by having approximately 3,700 gallons of 17 grainper gallon water run through it. The two cartridges used to treat thewater were arranged in series. The untreated water was just 17 grain pergallon water.

The treated and untreated water were circulated through a reverseosmosis system containing a BW30 membrane, commercially available fromDow. The membrane tested had a surface area of 0.5 feet by 0.5 feet. Thetreated and untreated water was passed through the membrane system at aconstant pressure of 400 PSI. The temperature of the water wasmaintained at between 70° F. and 76° F. Samples were taken 4 to 5 timesa day, and tested for the total dissolved solids (TDS) concentration.The permeate flow was also measured.

The results from this test are shown in FIG. 7 (Concentrate TDS vs.Total Time) and FIG. 8 (Scatterplot of Permeate vs. Total Time). Theconcentrate water by definition is the water and solids rejected by themembrane i.e. the material not passed through the membrane. As amembrane gets fouled or plugged, the TDS of the concentrate willdecrease because the membrane is not passing as much water as before themembrane was fouled. As described below, at the same time that the TDSof the concentrate is decreasing, the permeate flow though the membranewill also decrease with fouling as explained below.

In this experiment, the fouling of the membrane exposed to the untreatedwater progressed to where it was severely plugged as indicated by thedecrease in concentrate TDS. Fouling of a membrane from hard waterscaling is a known problem when using a membrane in hard water. Thechemical analysis of the membrane exposed to the untreated waterconfirmed that the untreated membrane was fouled with calcium carbonatescale.

As can be seen from FIG. 7, the amount of TDS in the concentrate waterdecreased over time with the untreated water, and remained relativelyconstant with the treated water. That is, the membrane exposed to thetreated hard water showed no decrease in TDS throughout the 28 hourexperiment, indicating that the treated water protected the membranefrom scaling.

As can be seen from FIG. 8, the permeate flow rate declines at a fasterrate using untreated water compared to the treated water. It is thoughtthat this is due to calcium carbonate and other insoluble saltsprecipitating on the membrane more slowly when using the treated watercompared to the untreated water. This water hardness scale precipitationbuilds up and gradually restricts the flow of water through the membrane(permeate flow). The buildup of scale on the membrane that had untreatedwater circulated through it was so severe in this test that the permeateflow was reduced to nearly one-half of the starting flow rate, as seenin FIG. 8.

Overall, it was found that using water treated with an apparatusaccording to embodiments of the present invention lead to a decrease inscaling when circulated through a reverse osmosis system.

Example 7

A test was run to evaluate the pH and total dissolved solids content ofwater when passed through an apparatus in accordance with embodiments ofthe present invention compared to traditional water treatment media. Thefollowing resins/media were tested: Resin A was a Lanxess S-8528 resin,commercially available from Lanxess, that had been exhausted by havingpreviously been used for 5,000 cycles of 9 seconds on 27 seconds offwith 17 gpg cold water at a flow rate of four gallons per minute; MediaB was a slightly used Watts media, commercially available from WattsWater Technologies; and Media C was an unused Watts media, commerciallyavailable from Watts Water Technologies. A control was also run, withoutany resin or media for comparison.

17 gpg water was cycled through the test resins/media for ten secondson, and two minutes off. The water was passed through the testresins/media at a rate of one gallon per minute during the on cycle.Samples were taken at the same time from each test resin/media, andimmediately evaluated for pH and TDS. The results are shown in FIGS. 9and 10.

As can be seen in FIG. 9, the pH of the water treated with Resin Aremained relatively constant throughout treatment and closely matchedthat of the control. The pH of the water treated with Media B and C wassignificantly lower at first and then increased over time. Likewise, asshown in FIG. 10, the TDS of the water treated with Resin A remainedrelatively constant and equal to the control throughout treatment. TheTDS of the water treated with Media B and C was significantly lower andgenerally increased over time with usage. Without wishing to be bound byany particular theory, it is thought that the gradual increase in TDSand pH for Media B and C over time is due to those media being used andgradually losing their efficacy over time with usage. When Media B and Care not used for a period of time, i.e. a resting period, the drop in pHand TDS returns as seen in the last data points in FIGS. 9 and 10.

It is also thought that the immediate drop in pH and TDS of watertreated with Media B and C is the result of calcium carbonateprecipitating out of the water as caused by this particular media. Thewater changes are chemically explained by the removal of calcium andcarbonate ions from the water and the simultaneous addition of CO2 intothe water. These side-effects of precipitation are documented inliterature available from the manufacturer of the media.

Overall it was found that water treated with a resin in accordance withembodiments of the present invention, Resin A, the pH and the TDS of thewater did not substantially deviate from the control. This indicatesthat resin A is not causing precipitation of hardness in the water.

Example 8

A test was run to evaluate the effect of adding an oxidant to a watertreatment apparatus. For this test, chlorine was used as an oxidant, andwas tested at two concentrations, 1 ppm and 10 ppm. The addition of theoxidant was also evaluated when added before or after the water wastreated by the resin. The test also evaluated of the effects of theaddition of a carbon filter before or after the resin. The resin testedwas Lanxess Lewatit S-8528. The resin was pre-conditioned for 5500cycles of 9 seconds on 27 seconds off with 17 gpg cold water at 4gallons per minute

Two tests were run, one to measure performance, and one to measure thetotal organic carbon (TOC) of the water. For the performance test, adoor type dishmachine (Hobart AM-15) was used. The selected treatmentapparatus was connected to the water inlet of the dishmachine so thatall of the water for the machine was treated. The inlet water had ahardness of 17 grains. Glassware was placed inside the dishmachine in aglassware rack. The machine was run normally for 130 cycles. Nochemicals, e.g., detergents, rinse aids, other than the water treatmentapparatuses, and the addition of an oxidant, chlorine, were used in thistest. After the 130 cycles were complete, the glassware was removed andallowed to air dry. Photos of the glasses were taken. A light box wasalso used to determine reflectance which is a direct correlation to theamount of scale present. That is, a lower score correlates to less scalepresent on the glasses.

The results of a test including 1 ppm of chlorine added either before orafter the water passes through the treatment apparatus, and with orwithout the use of an additional carbon filter are shown in FIG. 11.FIG. 12 shows the results of a test including 10 ppm of chlorine addedeither before or after the water passes through the treatment apparatus,and with or without the use of an additional carbon filter.

As can be seen from these figures, an increase in the level of chlorinebefore the water treatment apparatus boosts the performance of the watertreatment apparatus in a dish machine test. The effect was furtherpronounced at higher levels of chlorine (10 Ppm).

The ppm TOC of the sample was also measured with a GE Sievers 900laboratory TOC analyzer. The results are shown in FIG. 13 (1 ppmchlorine added) and FIG. 14 (10 ppm chlorine added). As can be seen fromthese figures, the increase in chlorine level to 10 ppm before the resinalso increases the TOC level regardless of carbon filter location. Whenchlorine is added before the resin, the chlorine will contact the resinand act as an oxidant to the resin. As can be seen in FIG. 14, 10 ppm ofchlorine before the resin increased the TOC levels compared to adding 10ppm chlorine after the resin.

Another test was run to evaluate the effects of different oxidants onthe water treatment apparatus. For this test, the following resins wereincluded in the water treatment apparatuses: Lanxess Lewatit S-8528,commercially available from Lanxess; IRC-76, commercially available fromDow; Purolite C107, commercially available from the PuroliteCorporation; and Dow MAC-3, commercially available from Dow. The resinswere pre-conditioned by running cold water for 2,400 cycles through theresins. Each cycle consisted of 9 seconds run time followed by 27seconds off with 17 gpg cold water at 4 gallons per minute. For thisshake up test, 5 grams of the wet resin was put into 40 grams of watersolutions containing the selected oxidants, then shaken up by hand for10 seconds, and then submerged in the same solutions overnight. Theoxidants in this test included: 150 ppm C10, and 150 ppm H2O2. Thesolutions were shaken again before filtration. The TOC of the filteredmaterial was measured.

The results of this test are shown in FIG. 15. As can be seen from FIG.15, the addition of either oxidant boosted the level of TOC in each ofthe filtrates. Without wishing to be bound by any particular theory, itis believed that the Mac-3 resin has a much lower relative TOC becauseit is more a highly crosslinked resin. TOC levels are known in the artto be inversely related to crosslinking percentages.

Another test was run to further evaluate the effects of the addition ofchlorine in a shake-up test. For this test, the following resins wereincluded in the water treatment apparatuses: Lanxess Lewatit S-8528,commercially available from Lanxess; IRC-76, commercially available fromDow; Purolite C107, commercially available from the PuroliteCorporation; and Dow MAC-3, commercially available from Dow. The resinswere pre-conditioned by running cold water for 2,400 cycles through theresins. For this shake up test, 5 grams of the wet resin and 40 grams ofwater were shaken together on an automatic shaker for 10 minutes. Either5 ppm, or 10 ppm of chlorine, or no chlorine (control) was added to thewater. After the ten minutes, the water was filtered and the TOC wasmeasured. The results from this test are shown in FIG. 16. As can beseen from this Figure, the addition of chlorine did boost the TOC levelsfor three out of the four resins tested. Without wishing to be bound bya particular theory, it is believed that the Mac-3 resin has a muchlower TOC because it is a more highly crosslinked resin.

Example 9

A test was run to measure the limescale build up control on glassesusing various water treatment apparatuses containing exhausted resinmaterial. Each of the resins tested was previously exhausted by running17 grain cold water for about 6,600 cycles on a laboratory test rig.Each conditioning cycle consisted of 9 seconds run time followed by 27seconds off with 17 gpg cold water at 4 gallons per minute. The resinstested included the following: Lanxess Lewatit S-8528, commerciallyavailable from Lanxess; IRC-76, commercially available from Dow;Purolite C107, commercially available from the Purolite Corporation; DowMAC-3, commercially available from Dow; and Watts OneFlow II,commercially available from Watts Water Technologies.

The test was run using a door type dishmachine (Hobart AM-15). Theselected test apparatus was connected to the inlet water to thedishmachine so that all of the water for the machine was treated. Theinlet water had a hardness of 17 grains. The test was run for 100continuous cycles. Each cycle consisted of: 45 second wash at 160° F.,10 second wash at 186° F., and a 20 second dwell or rest between cycles. . . .

Glassware was placed inside the dishmachine in a glassware rack. Themachine was run normally for 100 cycles. No chemicals, e.g., detergents,rinse aids, other than the treatment apparatuses were used in this test.After the 100 cycles were complete, the glassware was removed andallowed to air dry. Photos of the glasses were taken. A light box wasalso used to determine reflectance which is a direct correlation to theamount of scale present.

The results are shown in FIG. 17. As can be seen from this figure, theexhausted IRC-76 and Lanxess materials performed the best in thedishmachine, i.e., had the least amount of scaling. The first fourresins in FIG. 17 are each polyacrylate weak acid cation exchange resinspre-conditioned to exhaustion. As can be seen, the anti-scalingperformance in this test varies widely from poor (Mac-3) to fair (C107)to good (IRC-76 and S-8528). Without wishing to be bound by anyparticular theory, it is thought that the chemical differences betweenthese resins lead to the differences in performance. The resincrosslinking percentages is one such difference, as exemplified by theMac-3 resin, which is assumed to have a relatively high level ofcrosslinking as indicated by its rather low TOC levels (FIGS. 15 and16).

Example 10

Various resin samples were pre-conditioned by running cold, 17 gpg,water for 23,000 cycles through the resin, followed by 30,000 cycles ofhot, 17 gpg, water. The resins tested included the following: LanxessLewatit S-8528, commercially available from Lanxess; IRC-76,commercially available from Dow; Purolite C107, commercially availablefrom the Purolite Corporation; Dow MAC-3, commercially available fromDow; and Watts OneFlow II, commercially available from Watts WaterTechnologies. Each cycle consisted of 9 seconds of run time, followed by27 seconds off. Thirty grams of wet resin were put into 25 g ofultrapure water, and shaken up overnight. The samples were then filteredand submitted for Gel Permeation Chromatography (GPC).

The samples were run on a Viscotek GPCmax equipped with a TriSECdetector array. Fifty microliters of each sample was injected into theaqueous GPC system using only refractive index detection to determinethe apparent concentration. The results are shown in FIG. 18A. As can beseen in this Figure, the chromatograph shows a lower concentration ofextractables than the IRC-76. The retention time on the chromatograph isconsistent with a less than 10,000 molecular weight polyacrylatestandard.

In this testing, assuming the detector response is similar for eachpolymer tested, the apparent concentration of the extracted substancefrom the Dow MAC-3 resin was measurably lower than any of the othertested resin extracts. These results are in agreement with the TOCanalysis (discussed in Example 8), which showed Dow MAC-3 had the lowestcarbon content when compared to all other tested resins. The GPC testingalso shows that the carbon content is present as a low molecular weightpolymer, as opposed to a low molecular weight hydrocarbon. FTIR analysisconfirmed that the polymer is most likely a polyacrylate species.

Overall, this study, in combination with application testing,demonstrates that a minimum concentration of TOC/polymer is necessaryfor function. When the concentration of extractables is too low, as withthe Dow MAC-3, shown by the TOC and GPC testing, the application testingresults are also poor, as shown in Example 9.

OTHER EMBODIMENTS

It is to be understood that while the invention has been described inconjunction with the detailed description thereof, the foregoingdescription is intended to illustrate, and not limit the scope of theinvention, which is defined by the scope of the appended claims. Otheraspects, advantages, and modifications are within the scope of thefollowing claims.

In addition, the contents of all patent publications discussed supra areincorporated in their entirety by this reference.

It is to be understood that wherever values and ranges are providedherein, all values and ranges encompassed by these values and ranges,are meant to be encompassed within the scope of the present invention.Moreover, all values that fall within these ranges, as well as the upperor lower limits of a range of values, are also contemplated by thepresent application.

1: A method for treating water comprising: contacting a water source with a water treatment composition comprising a substantially water insoluble resin material loaded with a plurality of one or more multivalent cations, such that the water is treated, wherein the substantially water insoluble resin is exhausted so that it is unable to perform ion exchange. 2: The method of claim 1, wherein the resin material comprises a weak acid cation resin.
 3. (canceled) 4: The method of claim 1, wherein the multivalent cations comprise a mixture of calcium and magnesium ions. 5: The method of claim 1, wherein the composition does not precipitate water hardness ions out of the source of water when contacted with the water. 6: The method of claim 1, wherein the step of contacting comprises passing the water through a treatment reservoir containing the composition. 7: The method of claim 1, further comprising agitating the composition during the contacting step, heating the water source prior to the contacting step, and/or increasing the pH of the water source prior to the contacting step. 8-10. (canceled) 11: The method of claim 1, wherein the treated water reduces scale formation on a surface contacted by the treated water. 12: The method of claim 1, wherein the resin material is selected from the group consisting of a gel type resin structure, a macroporous type resin structure, and combinations thereof.
 13. (canceled) 14: The method of claim 1, wherein the weak acid cation resin is selected from the consisting of a crosslinked acrylic acid polymer, a crosslinked methacrylic acid polymer, and mixtures thereof. 15-19. (canceled) 20: A method for reducing scale formation in an aqueous system comprising: contacting the aqueous system with a composition comprising a substantially water insoluble weak acid cation resin material loaded with a plurality of multivalent cations, such that scale formation in the aqueous system is reduced; wherein the substantially water insoluble weak acid cation resin is exhausted so that it is unable to perform ion exchange. 21: The method of claim 20, wherein the step of contacting comprises passing the water through a treatment reservoir containing the composition. 22: The method of claim 20, further comprising agitating the composition during the contacting step, heating the water source prior to the contacting step, and/or increasing the pH of the water source prior to the contacting step. 23: The method of claim 20, wherein the weak acid cation resin material is selected from the group consisting of a gel type resin structure, a macroporous type resin structure, and combinations thereof. 24: The method of claim 20, wherein the weak acid cation resin is selected from the consisting of a crosslinked acrylic acid polymer, a crosslinked methacrylic acid polymer, and mixtures thereof. 25: The method of claim 24, wherein resin polymers have additional copolymers added selected from the group consisting of butadiene, ethylene, propylene, acrylonitrile, styrene, vinylidene chloride, vinyl chloride, and derivatives and mixtures thereof. 26: The method of claim 24, wherein the acrylic acid polymer is crosslinked with a polyvinyl aromatic composition selected from the group consisting of polyvinyl aromatics such as divinyl benzene, trivinyl benzene, divinyl toluene, divinyl xylene, polyvinyl anthracene, and derivatives and mixtures thereof. 27: A method for treating water comprising: contacting a water source with a water treatment composition such that the water is treated; wherein the water treatment composition consisting essentially of a substantially water insoluble weak acid cation resin material; wherein the substantially water insoluble weak acid cation exchange resin is loaded with a plurality of one or more multivalent cations, wherein the substantially water insoluble weak acid cation exchange resin is exhausted so that it is unable to perform ion exchange, wherein the substantially water insoluble weak acid cation exchange resin is selected from the group consisting of a gel type resin structure, a macroporous type resin structure, and combinations thereof, and wherein the substantially water insoluble weak acid cation exchange resin comprises a polymer selected from the group consisting of a crosslinked acrylic acid polymer, a crosslinked methacrylic acid polymer, and mixtures thereof. 28: The method of claim 27, further comprising agitating the composition during the contacting step, heating the water source prior to the contacting step, and/or increasing the pH of the water source prior to the contacting step. 29: The method of claim 27, wherein the acrylic acid polymer is crosslinked with a polyvinyl aromatic composition selected from the group consisting of polyvinyl aromatics such as divinyl benzene, trivinyl benzene, divinyl toluene, divinyl xylem, polyvinyl anthracene, and derivatives and mixtures thereof. 30: The method of claim 27, wherein the step of contacting comprises passing the water through a treatment reservoir containing the water treatment composition. 